Compositions for oxidatively dyeing keratin fibers and methods for using such compositions

ABSTRACT

Compositions for dyeing keratin fibers comprise (a) at least one keratin dyeing compound selected from aromatic systems which comprise at least one boronic acid or boronic ester moiety and which are capable of forming upon oxidation a nucleophile or an electrophile, (b) at least one additional keratin dyeing compound selected from the group consisting of auxiliary developers and auxiliary couplers, and (c) a cosmetically suitable medium. Methods for oxidatively dyeing keratin fibers comprise the steps of applying such compositions in the presence of an oxidizing agent and rinsing the hair. A hair coloring product in kit form comprises a first separately packaged container comprising a composition as described above and a second separately packaged container comprising an oxidizing agent.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional application Ser.No. 60/779,779 filed on Mar. 7, 2006.

FIELD OF THE INVENTION

The present invention relates to compositions for oxidatively dyeingkeratin fibers and methods for using such compositions. Moreparticularly, the present invention relates to such compositionscomprising aromatic systems which comprise at least one boronic acid orboronic ester moiety and which are capable of forming upon oxidation anucleophile or an electrophile.

BACKGROUND OF THE INVENTION

The most extensively used method currently employed to dye keratinfibers, such as hair, is by an oxidative process that utilizes one ormore oxidative dye compounds in combination with one or more oxidizingagents.

Commonly, a peroxy oxidizing agent is used in combination with one ormore developers or couplers, which are generally small molecules capableof diffusing into hair. A wide variety of oxidants may be used togenerate the reactive developer species. Generally, a peroxide material,such as hydrogen peroxide, activates the developers so that they reactwith the couplers to form larger sized compounds in the hair shaft togive a variety of shades and colors.

A wide variety of developers and couplers have been employed in suchoxidative hair coloring systems and compositions. However, there stillexists a need for additional keratin dyeing compounds which can act asdevelopers and/or couplers and which can safely provide color benefits.

Hydrogen peroxide-mediated transformation of arylboronic acids orarylboronic esters to phenols has been investigated to develop highlyselective and sensitive probes for hydrogen peroxide, which is one ofthe major reactive oxygen species (“ROS”) in living cells. The kineticsof the reaction between hydrogen peroxide and phenylboronic acid wasinvestigated by Henry G. Kuivila et al., J. Am. Chem. Soc. 1957, 79,5659, who proposed the following mechanism:

Additionally, the transformation of boronic acids and boronic esters tothe corresponding alcohols by the use of Oxone™ in aqueous acetonebuffered with sodium bicarbonate has been described by Kevin S. Webb etal., Tetrahedron Letters, 1995, 36, 5117.

More recently, the syntheses and biological applications of fluorescentprobes for hydrogen peroxide have been reported by Michelle C. Y. Changet al., J. Am Chem. Soc., 2004, 126, 15392 and 2005, 127, 16652. Theseperoxysensors utilize a boronate-hydrogen peroxide reaction to providehigh selectivity for detecting hydrogen peroxide in aqueous solution.The boronate compound is non-fluorescent and displays no absorption inthe visible region. The addition of hydrogen peroxide triggers immediateincrease in fluorescence and growth of visible wavelength absorptionbands characteristic fluorescein and red-fluorescent resorufin, as shownin the following mechanisms, respectively:

The aforementioned references, however, do not disclose the use of suchboronic acid and boronic ester compounds in compositions for oxidativelydyeing keratin fibers.

It has now been discovered that certain aromatic systems comprising atleast one boronic acid or boronic ester moiety are capable of impartingcommercially desirable colors to keratin fibers, such as hair. Suchboronic acid or boronic ester compounds are capable of providing dyeingresults comparable, in terms of color and intensity, to those achievedby using known oxidative dye compounds. Accordingly, there exists a needfor keratin fiber dyeing compositions which comprise aromatic systemscomprising at least one boronic acid or boronic ester moiety.

SUMMARY OF THE INVENTION

The present invention relates to compositions for dyeing keratin fibers,the compositions comprising (a) at least one keratin dyeing compoundselected from aromatic systems which comprise at least one boronic acidor boronic ester moiety and which are capable of forming upon oxidationa nucleophile or an electrophile, (b) at least one additional keratindyeing compound selected from the group consisting of auxiliarydevelopers and auxiliary couplers, and (c) a cosmetically suitablemedium. The keratin dyeing compounds of the present invention, whichcomprise a boronic acid or boronic ester moiety, may act as a coupler oras a developer or may self-couple to produce a color in keratin fibers.

The present invention further relates to a method for oxidatively dyeingkeratin fibers, the method comprising the steps of applying suchcompositions in the presence of an oxidizing agent and rinsing the hair.

The present invention also further relates to a kit for treating hair,the kit comprising a first separately packaged container comprising acomposition of the present invention and a second separately packagedcontainer comprising an oxidizing agent.

DETAILED DESCRIPTION OF THE INVENTION

While the specification concludes with claims that particularly pointout and distinctly claim the invention, it is believed the presentinvention will be better understood from the following description.

As used herein, “comprising” means that other steps and otheringredients which do not affect the end result can be added. This termencompasses the terms “consisting of” and “consisting essentially of”.The compounds/compositions and methods/processes of the presentinvention can comprise, consist of, and consist essentially of theessential elements and limitations of the invention described herein, aswell as any of the additional or optional ingredients, components,steps, or limitations described herein.

All percentages, parts and ratios are based upon the total weight of thecompositions of the present invention, unless otherwise specified. Allsuch weights as they pertain to listed ingredients are based on theactive level, and, therefore, do not include solvents or by-productsthat may be included in commercially available materials, unlessotherwise specified. The term “weight percent” may be denoted as “wt. %”herein.

Except as otherwise noted, all amounts including part, percentages, andproportions are understood to be modified by the word “about”, andamounts are not intended to indicate significant digits. Except asotherwise noted, the articles “a”, “an”, and “the” mean “one or more”.

As used herein, the term “keratin” refers to a scleroprotein found inepidermal tissues and modified into hard structures such as horns, hair,and nails. Thus, the term “keratin fibers” or “keratinous fibers” refersto those found in hair, skin and nails, and various animal body partssuch as horns, hooves and feathers.

As used herein, the term “hair” refers to keratinous fibers on a living(e.g., a person) or non-living body (e.g., in a wig, hairpiece, or otheraggregation of non-living keratinous fibers). Mammalian, preferablyhuman, hair is a preferred. Notably, hair, wool, fur, and otherkeratinous fibers are suitable substrates for coloring by the compoundsand compositions described herein.

As used herein, the term “keratin dyeing compounds” refers to compoundsthat may be used in the composition to act as developers, couplers, orboth, in order to provide color to keratin fibers.

As used herein, the term “keratin dyeing composition” refers to thecomposition containing one or more keratin dyeing compounds, includingthe compounds described herein.

As used herein, “cosmetically acceptable” means that ingredients whichthe term describes are suitable for use in contact with the skin or hairof humans and lower animals without undue toxicity, incompatibility,instability, irritation, allergic response, and the like.

It is understood that within the scope of this invention, numerouspotentially and actually tautomeric compounds are involved. As a generalexample of tautomerism, 2-mercaptopyridine (I) exists under knownconditions in the pyridine-2-thione tautomer form (II).

It is to be understood that when this description refers to a particularstructure, all of the reasonable additional tautomeric structures areincluded. In the art, tautomeric structures are frequently representedby one single structure and the present invention follows this generalpractice.

The keratin dyeing compositions of the present invention comprise (a) atleast one keratin dyeing compound selected from aromatic systems whichcomprise at least one boronic acid or boronic ester moiety and which arecapable of forming upon oxidation a nucleophile or an electrophile, (b)at least one additional keratin dyeing compound selected from the groupconsisting of auxiliary developers and auxiliary couplers, and (c) acosmetically suitable medium. Each of these components, as well aspreferred and/or optional additional components, is described in detailhereinafter.

I. Compositions for Oxidatively Dyeing Keratin Fibers

A. Boronic Acid and Boronic Ester Keratin Dyeing Compounds

The compositions for dyeing keratin fibers of the present inventioncomprise at least one keratin dyeing compound selected from aromaticsystems which comprise at least one boronic acid or boronic ester moietyand and which are capable of forming upon oxidation a nucleophile or anelectrophile. As used herein, the term “aromatic system” refers to asubstituted mono- or poly-cyclic hydrocarbon ring which includes,optionally, one or more heteroatoms in the ring, and which has a cyclic,planar, and conjugated pi-electron system with the number of delocalizedpi-electrons being (4n+2) wherein n is an integer. As used herein, theterm “nucleophile” refers to a neutral or negatively charged chemicalspecies which is attracted to positive sources such as nuclei and whichtends to donate or share electrons in order to form a chemical bond. Asused herein, the term “electrophile” refers to a neutral or positivelycharged chemical species which is attracted to negative sources andwhich tends to accept electron pairs in order to form a chemical bond.

The aromatic systems of the present invention include, but are notlimited to, compounds according to one of the following formulas I toXV:

-   -   wherein R1, R2, R3, R4, R7, R8, R9, R10, R11, R12, and R13 each        are independently selected from the group consisting of:    -   (a) C-linked monovalent substituents selected from the group        consisting of:        -   (i) substituted or unsubstituted, straight or branched,            alkyl, mono- or poly-unsaturated alkyl, heteroalkyl,            aliphatic, heteroaliphatic, or heteroolefinic systems,        -   (ii) substituted or unsubstituted, mono- or poly-cyclic            aliphatic, aryl, or heterocyclic systems, and        -   (iii) substituted or unsubstituted, mono-, poly-hydroxy or            -fluoro alkyl systems;    -   wherein said systems of (i), (ii) and (iii) comprise from about        1 to about 10 carbon atoms and from about 0 to about 5        heteroatoms selected from the group consisting of O, S, N, P,        and Si;    -   (b) S-linked monovalent substituents selected from the group        consisting of SA¹,    -   (c) O-linked monovalent substituents selected from the group        consisting of OA¹;    -   (d) N-linked monovalent substituents selected from the group        consisting of NA¹A²;    -   (e) a halogen selected from the group consisting of F, Cl, Br,        and I;    -   (f) fluoroalkyl monovalent substituents selected from the group        consisting of mono-, poly-, and per-fluoro alkyl systems        comprising from about 1 to about 12 carbon atoms and from about        0 to about 4 heteroatoms; and    -   (g) hydrogen; and    -   wherein R is selected group consisting of hydrogen, COR1, and        said C-linked monovalent substituents of (a);    -   wherein R5 and R6 each are independently selected from the group        consisting of hydrogen and lower alkyl groups which can be        joined together as a straight or branched alkylene chain forming        a five or six-membered ring or an aromatic ring;    -   wherein X is selected from the group consisting of hydroxyl,        B(OR5)OR6, and NA1A2;    -   wherein Y and Z each are independently selected from the group        consisting of hydroxyl and B(OR5)OR6, provided that at least one        of which is B(OR5)OR6; and    -   wherein A¹ and A² are monovalent and are independently selected        from the group consisting of hydrogen; substituted or        unsubstituted, straight or branched, alkyl, mono- or        poly-unsaturated alkyl, heteroalkyl, aliphatic, heteroaliphatic,        or heteroolefinic systems; substituted or unsubstituted, mono-        or poly-cyclic aliphatic, aryl, or heterocyclic systems; and        substituted or unsubstituted, mono-, poly-, per-fluoro alkyl        systems; or A¹ and A² together with a nitrogen atom to which        they are bound form a ring; wherein all of said systems comprise        from about 1 to about 10 carbon atoms and from about 0 to about        5 heteroatoms selected from the group consisting of O, S, N, P,        and Si.

In one embodiment of the present invention, R1, R2, R3, R4, R7, R8, R9,R10, R11, R12, and R13 each are independently selected from the groupconsisting of a hydrogen atom; a halogen atom such as chlorine, bromine,iodine or fluorine; an amino radical, a hydroxyl radical; a cyanoradical; a C₁-C₄ alkyl radical; a trifluoromethyl radical, an alkylaminoradical (e.g., N,N-dimethylamino, N,N-diethylamino, N-methylamino, orN-ethylamino); a hydroxyalkylamino radical (e.g., N-(hydroxyethyl)amino,N-hydroxymethylamino, N-hydroxypropylamino, N,N-bis(hydroxyethyl)amino,N-(2,3-dihydroxypropyl)amino or N,N-bis(hydroxypropyl)amino); anacetylamido radical; a carboxyl radical; an alkoxy radical (e.g.,methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy, phenoxyethoxy,2-cyanoethoxy, phenethyloxy, phenoxyethoxy, p-chlorobenzyloxy ormethoxyethylcarbamoylmethoxy); an alkoxyalkyl radical (e.g.,methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl orethoxypropyl); a carbamoyl radical; an alkylcarbamoyl radical (e.g.,methylcarbamoyl, ethylcarbamoyl, dimethylcarbamoyl, ordiethylcarbamoyl); a hydroxyalkylcarbamoyl radical (e.g.,2-hydroxyethylcarbamoyl, bis(2-hydroxyethyl)carbamoyl,hydroxymethylcarbamoyl, bis(hydroxymethyl)carbamoyl); an amido radical;an alkylamido radical (e.g., acetamido, propionamido, or butyramido); analkylcarbonyl radical (e.g., acetyl, butyryl, or propionyl), analkoxycarbonyl radical (e.g., methoxycarbonyl, ethoxycarbonyl, orpropoxycarbonyl); an aryloxy radical (e.g., phenoxy, 4-methoxyphenoxy,4-nitrophenoxy, 4-cyanophenoxy, 4-methanesulfonamidophenoxy,4-methanesulfonylphenoxy, 3-methylphenoxy or 1-naphthyloxy); an acyloxyradical (e.g., acetoxy, propanoyloxy, benzolyloxy,2,4-dichlorobenzolyloxy, ethoxyalkyloxy, pyruviloyloxy, cinnamoyloxy ormyristoyloxy); an alkylthio radical (e.g., methylthio, ethylthio,propylthio, butylthio, 2-cyanoethylthio, benzylthio, phenethylthio,2-(diethylamino)ethylthio, ethoxyethylthio or phenoxyethylthio); anarylthio radical (e.g., phenylthio, 4-carboxyphenylthio,2-ethoxy-5-tert-butylphenylthio, 2-carboxyphenylthio or4-methanesulfonylphenylthio); a heteroarylthio radical (e.g.,5-phenyl-2,3,4,5-tetrazolyloxy or 2-benzothiazolyloxy); a heteroaryloxyradical (e.g., 5-phenyl-2,3,4,5-tetrazolyloxy or 2-benzothiazolyloxy); a5- or 6-membered heterocycle having at least one nitrogen, oxygen orsulfur atom (e.g., pyridyl, quinolyl, morpholyl, furyl, tetrahydrofuryl,pyrazolyl, triazolyl, tetrazolyl, triazolyl, oxazolyl, imidazolyl orthiadiazolyl) and being optionally substituted; an aryl radical (e.g.,phenyl or naphthyl) which is optionally substituted; a sulfonyl radical;a sulfinyl radical; a phosphonyl radical; a sulfamoyl radical; a siloxyradical; an acyloxy radical; a carbamoyloxy radical; a sulphonamideradical; an imide radical; a ureido radical; a sulfamoylamino radical;an alkoxycarbonylamino radical; an aryloxycarbonylamino radical; anaryloxycarbonyl radical; and a benzenesulfonamido radical.

The keratin dyeing compounds of the present invention which are aromaticsystems comprising at least one boronic acid or boronic ester moiety mayact upon oxidation as a coupler or as a developer or may self-couple toproduce a color in keratin fibers.

When utilized as a coupler, the compounds of the present invention mayaccommodate a nucleofugic leaving group at a potential couplingposition. Suitable nucleofugi leaving groups include, but are notlimited to, those selected from the group consisting of hydrogen,chlorine, cyano, alkoxy, phenoxy, methylsulfonyoxy, pyridine, andpyridazone.

In an embodiment of the present invention, the boronic acid or boronicester compounds of the present invention are couplers and are utilizedin compositions together with developers that are pyrazoles. In afurther embodiment, the couplers of the present invention are utilizedin compositions together with one or more of the following pyrazoledevelopers: 1-methyl-1H-pyrazole-4,5-diamine,2-(4,5-diamino-1H-pyrazol-1-yl)ethanol,1-isopropyl-1H-pyrazole-4,5-diamine,1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine,1-(benzyl)-1H-pyrazole-4,5-diamine,1-(4-chlorobenzyl)-1H-pyrazole-4,5-diamine and1-hydroxyethyl-4,5-diaminopyrazole sulfate. In a preferred embodiment,the couplers of the present invention are utilized in compositionstogether with at least one pyrazole developer compound selected from1-methyl-1H-pyrazole-4,5-diamine; 1-hydroxyethyl-4,5-diaminopyrazolesulfate; and 2-(4,5-diamino-1H-pyrazol-1-yl)ethanol. While not beingbound to theory, it is believed that such combinations enable thedesired achievement of more bathochromic colors (e.g., blue) relative toconventional combinations of developers and couplers.

Exemplified Compounds of Formulas I to XV

Non-limiting examples of keratin dyeing compounds selected from aromaticsystems comprising at least one boronic acid or boronic ester moiety,which are representative of compounds according to formulas I to XV ofthe present invention, are provided in the following.

1. Exemplified Compounds of Formula I

Exemplified compounds according to Formula I include, but are notlimited to, 3-hydroxyphenylboronic acid, 3-hydroxy-2-methylphenylboronicacid, 2-chloro-5-hydroxyphenylboronic acid,6-chloro-3-hydroxy-2-methylphenylboronic acid,3-hydroxy-6-methoxy-2-methylphenylboronic acid,3-hydroxy-2,4-dimethylphenylboronic acid, 2-ethyl-3-hydroxyphenylboronicacid, 3-hydroxy-2-(2-hydroxyethyl)phenylboronic acid,2-(2,2,2-trifluoroethyl)-3-hydroxyphenylboronic acid,2-(cyanomethyl)-3-hydroxyphenylboronic acid,3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol,2-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol,4-chloro-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol,4-chloro-2-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol,4-methoxy-2-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol,2,6-dimethyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol,2-ethyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol,2-(2-hydroxyethyl)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol,3-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)phenol,2-methyl-3-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)phenol,3-(benzo[d][1,3,2]dioxaborol-2-yl)phenol,3-(benzo[d][1,3,2]dioxaborol-2-yl)-2-methylphenol,3-(1,3,2-dioxaborolan-2-yl)phenol,3-(1,3,2-dioxaborolan-2-yl)-2-methylphenol, 3-aminophenylboronic acid,3-amino-2-methylphenylboronic acid, 3-(methylamino)phenylboronic acid,3-(2-hydroxyethylamino)phenylboronic acid,3-[bis(2-hydroxyethyl)amino]phenylboronic acid,3-morpholinophenylboronic acid, 3-(pyrrolidin-1-yl)phenylboronic acid,3-amino-4-chlorophenylboronic acid, 5-amino-2,4-dichlorophenylboronicacid, 5-amino-2-methoxyphenylboronic acid,3-amino-4-methoxyphenylboronic acid,3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzenamine,3-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)benzenamine,3-(1,3,2-dioxaborolan-2-yl)benzenamine, and3-(benzo[d][1,3,2]dioxaborol-2-yl)benzenamine.

2. Exemplified Compounds of Formula II

Exemplified compounds according to Formula II include, but are notlimited to, 2-aminophenylboronic acid, 2-amino-5-methylphenylboronicacid, 2-amino-5-ethylphenylboronic acid, 2-amino-4-chlorophenylboronicacid, 2-amino-4-methoxyphenylboronic acid,2-(2-hydroxyethylamino)phenylboronic acid,2-[bis(2-hydroxyethyl)amino]phenylboronic acid,2-morpholinophenylboronic acid, 2-(pyrrolidin-1-yl)phenylboronic acid,2-(methylamino)phenylboronic acid,2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzenamine,4-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzenamine,2-(1,3,2-dioxaborolan-2-yl)benzenamine,2-(benzo[d][1,3,2]dioxaborol-2-yl)benzenamine, and2-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)benzenamine.

3. Exemplified Compounds of Formula III

Exemplified compounds according to Formula III include, but are notlimited to, 3,4-dihydro-2H-benzo[b][1,4]oxazin-6-yl-6-boronic acid,3,4-dihydro-7-methyl-2H-benzo[b][1,4]oxazin-6-yl-6-boronic acid,7-ethyl-3,4-dihydro-2H-benzo[b][1,4]oxazin-6-yl-6-boronic acid,3,4-dihydro-7-methoxy-2H-benzo[b][1,4]oxazin-6-yl-6-boronic acid,6-(1,3,2-dioxaborolan-2-yl)-3,4-dihydro-2H-benzo[b][1,4]oxazine,6-(benzo[d][1,3,2]dioxaborol-2-yl)-3,4-dihydro-2H-benzo[b][1,4]oxazine,and3,4-dihydro-6-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-2H-benzo[b][1,4]oxazine.

4. Exemplified Compounds of Formula IV

Exemplified compounds according to Formula IV include, but are notlimited to, naphthalen-1-yl-1-boronic acid,2-methylnaphthalen-1-yl-1-boronic acid, 2-ethylnaphthalen-1-yl-1-boronicacid, 4-chloronaphthalen-1-yl-1-boronic acid,4-methoxynaphthalen-1-yl-1-boronic acid,4,4,5,5-tetramethyl-2-(naphthalen-4-yl)-1,3,2-dioxaborolane,4,4,5,5-tetramethyl-2-(2-methylnaphthalen-1-yl)-1,3,2-dioxaborolane,2-(naphthalen-4-yl)-1,3,2-dioxaborolane,2-(naphthalen-4-yl)benzo[d][1,3,2]dioxaborole,5,5-dimethyl-2-(naphthalen-4-yl)-1,3,2-dioxaborinane,7-methylnaphthalen-1-yl-1-boronic acid,6-methylnaphthalen-1-yl-1-boronic acid,8-methylnaphthalen-1-yl-1-boronic acid,2-(2,2,2-trifluoroethyl)naphthalen-1-yl-1-boronic acid, and2-(2-hydroxyethyl)naphthalen-1-yl-1-boronic acid.

5. Exemplified Compounds of Formula V

Exemplified compounds according to Formula V include, but are notlimited to, 1H-indol-4-yl-4-boronic acid,7-chloro-1H-indol-4-yl-4-boronic acid, 7-methoxy-1H-indol-4-yl-4-boronicacid, 2-methyl-1H-indol-4-yl-4-boronic acid,2,3-dimethyl-1H-indol-4-yl-4-boronic acid,5-methyl-1H-indol-4-yl-4-boronic acid, 1-methyl-1H-indol-4-yl-4-boronicacid, 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole,4-(1,3,2-dioxaborolan-2-yl)-1H-indole,4-(benzo[d][1,3,2]dioxaborol-2-yl)-1H-indole, and4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-1H-indole.

6. Exemplified Compounds of Formula VI

Exemplified compounds according to Formula VI include, but are notlimited to, 1H-indol-6-yl-6-boronic acid,2-methyl-1H-indol-6-yl-6-boronic acid,2,3-dimethyl-1H-indol-6-yl-6-boronic acid,7-methyl-1H-indol-6-yl-6-boronic acid, 1-methyl-1H-indol-6-yl-6-boronicacid, 5-chloro-1H-indol-6-yl-6-boronic acid,5-methoxy-1H-indol-6-yl-6-boronic acid,6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole,6-(1,3,2-dioxaborolan-2-yl)-1H-indole,6-(benzo[d][1,3,2]dioxaborol-2-yl)-1H-indole, and6-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-1H-indole.

7. Exemplified Compounds of Formula VII

Exemplified compounds according to Formula VII include, but are notlimited to, 5-hydroxy-1H-indol-6-yl-6-boronic acid,6-hydroxy-1H-indol-5-yl-5-boronic acid,5-hydroxy-2-methyl-1H-indol-6-yl-6-boronic acid,6-hydroxy-2-methyl-1H-indol-5-yl-5-boronic acid,5-hydroxy-2,3-dimethyl-1H-indol-6-yl-6-boronic acid,6-hydroxy-2,3-dimethyl-1H-indol-5-yl-5-boronic acid,5-hydroxy-1-methyl-1H-indol-6-yl-6-boronic acid,6-hydroxy-1-methyl-1H-indol-5-yl-5-boronic acid,5-hydroxy-1-(2-hydroxyethyl)-1H-indol-6-yl-6-boronic acid,6-hydroxy-1-(2-hydroxyethyl)-1H-indol-5-yl-5-boronic acid,6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indol-5-ol,5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indol-6-ol,6-(1,3,2-dioxaborolan-2-yl)-1H-indol-5-ol,5-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-1H-indol-6-ol,2-methyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indol-5-ol,and2-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indol-6-ol.

8. Exemplified Compounds of Formula VIII

Exemplified compounds according to Formula VII include, but are notlimited to, 1-ethyl-3-(methylamino)-1H-pyrazol-5-yl-5-boronic acid,1-(2-hydroxyethyl)-3-(methylamino)-1H-pyrazol-5-yl-5-boronic acid,3-acetamido-1-(2-hydroxyethyl)-1H-pyrazol-5-yl-5-boronic acid,3-(2-hydroxyethylamino)-1-(2-hydroxyethyl)-1H-pyrazol-5-yl-5-boronicacid, 1-methyl-3-(methylamino)-1H-pyrazol-5-yl-5-boronic acid,5-(1,3,2-dioxaborolan-2-yl)-N, 1-dimethyl-1H-pyrazol-3-amine,2-(3-(ethylamino)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazol-1-yl)ethanol,N-(1-(2-hydroxyethyl)-5-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-1H-pyrazol-3-yl)acetamide,3-amino-1-phenyl-1H-pyrazol-5-yl-5-boronic acid, andN-(5-(benzo[d][1,3,2]dioxaborol-2-yl)-1-(2-hydroxyethyl)-1H-pyrazol-3-yl)acetamide.

9. Exemplified Compounds of Formula IX

Exemplified compounds according to Formula IX include, but are notlimited to, 4-amino-1-methyl-1H-pyrazol-5-yl-5-boronic acid,4-amino-1-ethyl-1H-pyrazol-5-yl-5-boronic acid,4-amino-1-(2-hydroxyethyl)-1H-pyrazol-5-yl-5-boronic acid,4-amino-1-(2-hydroxyethyl)-3-methyl-1H-pyrazol-5-yl-5-boronic acid,4-amino-1-benzyl-1H-pyrazol-5-yl-5-boronic acid,4-amino-1-isopropyl-1H-pyrazol-5-yl-5-boronic acid,5-(1,3,2-dioxaborolan-2-yl)-1-methyl-1H-pyrazol-4-amine,5-(1,3,2-dioxaborolan-2-yl)-1-ethyl-1H-pyrazol-4-amine,2-(4-amino-5-(1,3,2-dioxaborolan-2-yl)-1H-pyrazol-1-yl)ethanol,2-(4-amino-5-(1,3,2-dioxaborolan-2-yl)-3-methyl-1H-pyrazol-1-yl)ethanol,1-benzyl-5-( 1,3,2-dioxaborolan-2-yl)-1H-pyrazol-4-amine,5-(1,3,2-dioxaborolan-2-yl)-1-isopropyl-1H-pyrazol-4-amine,1-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazol-4-amine,1-ethyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazol-4-amine,2-(4-amino-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazol-1-yl)ethanol,2-(4-amino-5-(1,3,2-dioxaborolan-2-yl)-3-methyl-1H-pyrazol-1-yl)ethanol,1-methyl-5-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-1H-pyrazol-4-amine,1-ethyl-5-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-1H-pyrazol-4-amine,2-(4-amino-5-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-1H-pyrazol-1-yl)ethanol,2-(4-amino-3-methyl-5-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-1H-pyrazol-1-yl)ethanol,1-benzyl-5-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-1H-pyrazol-4-amine,and1-isopropyl-5-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-1H-pyrazol-4-amine.

10. Exemplified Compounds of Formula X

Exemplified compounds according to Formula X include, but are notlimited to, 4-aminophenylboronic acid, 4-amino-3-methylphenylboronicacid, 4-amino-3-ethylphenylboronic acid, 4-(methylamino)phenylboronicacid, 4-(2-hydroxyethylamino)phenylboronic acid,4-amino-3-chlorophenylboronic acid, 4-amino-3-methoxyphenylboronic acid,4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzenamine,2-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzenamine,4-(1,3,2-dioxaborolan-2-yl)benzenamine,4-(benzo[d][1,3,2]dioxaborol-2-yl)benzenamine, and4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)benzenamine.

11. Exemplified Compounds of Formula XI

Exemplified compounds according to Formula XI include, but are notlimited to, 3-aminopyridin-2-yl-2-boronic acid,3-(methylamino)pyridin-2-yl-2-boronic acid,3-amino-5-chloropyridin-2-yl-2-boronic acid,3-amino-5-methoxypyridin-2-yl-2-boronic acid,3-(2-hydroxyethylamino)pyridin-2-yl-2-boronic acid,3-[bis(2-hydroxyethyl)amino]pyridin-2-yl-2-boronic acid,3-morpholinopyridin-2-yl-2-boronic acid,3-(pyrrolidin-1-yl)pyridin-2-yl-2-boronic acid,2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-3-amine,5-chloro-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-3-amine,5-methoxy-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-3-amine,N-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-3-amine,2-(1,3,2-dioxaborolan-2-yl)pyridin-3-amine,2-(benzo[d][1,3,2]dioxaborol-2-yl)pyridin-3-amine, and2-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)pyridin-3-amine.

12. Exemplified Compounds of Formula XII

Exemplified compounds according to Formula XII include, but are notlimited to, 1H-indol-3-yl-3-boronic acid,5-amino-1H-indol-3-yl-3-boronic acid,5,6-dimethoxy-1H-indol-3-yl-3-boronic acid,5H-[1,3]dioxolo[4,5-f]indol-7-yl-7-boronic acid,5-amino-1H-indol-3-yl-3-boronic acid, 5-chloro-1H-indol-3-yl-3-boronicacid, 5-methoxy-1H-indol-3-yl-3-boronic acid,7-methoxy-1H-indol-3-yl-3-boronic acid, 4-fluoro-1H-indol-3-yl-3-boronicacid, 5-bromo-1H-indol-3-yl-3-boronic acid,4-methyl-1H-indol-3-yl-3-boronic acid, 6-methyl-1H-indol-3-yl-3-boronicacid, 3-(1,3,2-dioxaborolan-2-yl)-1H-indole,3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole,3-(4,5-dimethyl-1,3,2-dioxaborolan-2-yl)-1H-indole,3-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-1H-indole,3-(benzo[d][1,3,2]dioxaborol-2-yl)-1H-indole,5-bromo-3-(1,3,2-dioxaborolan-2-yl)-1H-indole,6-methoxy-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole, and5-methoxy-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole.

13. Exemplified Compounds of Formula XIII

Exemplified compounds according to Formula XIII include, but are notlimited to, 4-benzoyl-3-hydroxyphenylboronic acid,4-(3,5-diaminobenzoyl)-3-hydroxyphenylboronic acid,4-(3,5-dihydroxybenzoyl)-3-hydroxyphenylboronic acid,4-(2,4-dihydroxybenzoyl)-3-hydroxyphenylboronic acid,4-(2,4-diaminobenzoyl)-3-hydroxyphenylboronic acid,4-(2,5-diaminobenzoyl)-3-hydroxyphenylboronic acid,4-(2,5-dihydroxybenzoyl)-3-hydroxyphenylboronic acid,4-(2,6-diaminobenzoyl)-3-hydroxyphenylboronic acid,4-(2,6-dihydroxybenzoyl)-3-hydroxyphenylboronic acid,(4-(1,3,2-dioxaborolan-2-yl)-2-hydroxyphenyl)(phenyl)methanone,(3,5-diaminophenyl)(2-hydroxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)methanone,(4-(1,3,2-dioxaborolan-2-yl)-2-hydroxyphenyl)(3,5-dihydroxyphenyl)methanone,(2-hydroxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)(2,4-dihydroxyphenyl)methanone,(4-(1,3,2-dioxaborolan-2-yl)-2-hydroxyphenyl)(2,4-diaminophenyl)methanone,and(2-hydroxy-4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)phenyl)(3,5-dihydroxyphenyl)methanone.

14. Exemplified Compounds of Formula XIV

Exemplified compounds according to Formula XIV include, but are notlimited to, 2-benzoyl-3-hydroxyphenylboronic acid,2-(3,5-diaminobenzoyl)-3-hydroxyphenylboronic acid,2-(3,5-dihydroxybenzoyl)-3-hydroxyphenylboronic acid,(2-(1,3,2-dioxaborolan-2-yl)-6-hydroxyphenyl)(phenyl)methanone,(3,5-diaminophenyl)(2-hydroxy-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)methanone,(2-hydroxy-6-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)phenyl)(3,5-dihydroxyphenyl)methanone,(2,5-diaminophenyl)(2-hydroxy-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)methanone,and(2-hydroxy-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)(2,5-dihydroxyphenyl)methanone.

15. Exemplified Compounds of Formula XV

Exemplified compounds according to Formula XV include, but are notlimited to, 2,5,6-triaminopyrimidin-4-yl-4-boronic acid,6-(1,3,2-dioxaborolan-2-yl)pyrimidine-2,4,5-triamine,6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrimidine-2,4,5-triamine,6-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)pyrimidine-2,4,5-triamine, and6-(benzo[d][1,3,2]dioxaborol-2-yl)pyrimidine-2,4,5-triamine.

SYNTHESIS EXAMPLES

The following are non-limiting examples of synthesis of boronic acid orboronic ester compounds of the present invention.

Example A Synthesis of 3-aminophenylboronic acid and 3-hydroxyphenylboronic acid

The hydrogenation of m-nitrophenylboronic acid 1 in MeOH-water withplatinum oxide (PtO₂) at 60 psi hydrogen for 45 min affords3-aminophenyl boronic acid 2. Compound 2 was converted to3-hydroxyphenyl boronic acid 3 by diazotization with sodiumnitrite/sulfuric acid followed by hydrolysis (Bean, F. R., Johnson, J.R. J. Am. Chem. Soc. 1932, 54, 4415).

Example B Synthesis of 1-naphthaleneboronic acid

A mixture of 1-bromonaphthalene 1, magnesium powder in THF is irradiatedfor 15 min to produce Grignard reagent 2 which reacts with tributylborate to yield the boronic ester 3. Hydrolysis of 3 with aqueoussulfuric acid affords 1-naphthalene boronic acid 4 (Song, Y; Ding, Z;Wang, Q; Tao, F. Syn. Comm. 1998, 28, 3757, WO 9964428).

Example C Synthesis of3-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenol

Benzylation of 3-bromophenol 1 with benzyl chloride and potassiumcarbonate in DMF affords compound 2. Palladium (0)-catalyzedcross-coupling reaction of 2 with bis(pinacolato)diboron, PdCl₂(dppf),and potassium carbonate in DMSO at 80° C. gives rise to compound 3(Ishiyama, T; Murata, M; Miyaura, N. J. Org. Chem. 1995, 60, 7508).Debenzylation of 3 with Pd/C at 60 psi hydrogen in MeOH produces thetarget compound 4 (Pennington, T. E.; Kardiman, C; Hutton, C. A.Tetrahedron Lett. 2004, 45, 6657).

B. Auxiliary Developers and Auxiliary Couplers

The compositions for dyeing keratin fibers of the present inventioncomprise at least one additional keratin dyeing compound selected fromauxiliary developers and auxiliary couplers. As used herein, the terms“auxiliary developer” and “auxiliary coupler” respectively refer to anyknown oxidative keratin dyeing developer (i.e., primary intermediate)compound and any known oxidative keratin dyeing coupler compound, otherthan those boronic acid or boronic ester compounds of the presentinvention described above.

1. Auxiliary Developers

Suitable auxiliary developers for use in the compositions describedherein include, but are not limited to, p-phenylenediamine derivativessuch as: benzene-1,4-diamine (commonly known as p-phenylenediamine),2-methyl-benzene-1,4-diamine, 2-chloro-benzene-1,4-diamine,2-thiazole-2-yl-benzene-1,4-diamine,2-(6-methyl-pyridin-2-yl)-benzene-1,4-diamine,3′-fluoro-biphenyl-2,5-diamine, 2-propenyl-2-yl-benzene-1,4-diamine,N-phenyl-benzene-1,4-diamine, N-(2-ethoxyethyl)benzene-1,4-diamine,2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol (commonly known asN,N-bis(2-hydroxyethyl)-p-phenylenediamine),(2,5-diamino-phenyl)-methanol, 1-(2′-Hydroxyethyl)-2,5-diaminobenzene,2-(2,5-diamino-phenyl)-ethanol, N-(4-aminophenyl)benzene-1,4-diamine,2,6-dimethyl-benzene-1,4-diamine, 2-isopropyl-benzene-1,4-diamine,1-[(4-aminophenyl)amino]-propan-2-ol, 2-propyl-benzene-1,4-diamine,1,3-bis[(4-aminophenyl)(2-hydroxyethyl)amino]propan-2-ol,N⁴,N⁴,2-trimethylbenzene-1,4-diamine, 2-methoxy-benzene-1,4-diamine,1-(2,5-diaminophenyl)ethane-1,2-diol, 2,3-dimethyl-benzene-1,4-diamine,N-(4-amino-3-hydroxy-phenyl)-acetamide, 2,6-diethylbenzene-1,4-diamine,2,5-dimethylbenzene-1,4-diamine, 2-thien-2-ylbenzene-1,4-diamine,2-thien-3-ylbenzene-1,4-diamine, 2-pyridin-3-ylbenzene-1,4-diamine,1,1′-biphenyl-2,5-diamine, 2-(methoxymethyl)benzene-1,4-diamine,2-(aminomethyl)benzene-1,4-diamine, 2-(2,5-diaminophenoxy)ethanol,N-[2-(2,5-diaminophenoxy)ethyl]-acetamide,N,N-dimethylbenzene-1,4-diamine, N,N-diethylbenzene-1,4-diamine,N,N-dipropylbenzene-1,4-diamine, 2-[(4-aminophenyl)(ethyl)amino]ethanol,2-[(4-amino-3-methyl-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol,N-(2-methoxyethyl)-benzene-1,4-diamine,3-[(4-aminophenyl)amino]propan-1-ol,3-[(4-aminophenyl)-amino]propane-1,2-diol,N-{4-[(4-aminophenyl)amino]butyl}benzene-1,4-diamine, and2-[2-(2-{2-[(2,5-diaminophenyl)-oxy]ethoxy}ethoxy)ethoxy]benzene-1,4-diamine,1,3-Bis(N(2-Hydroxyethyl)-N-(4-amino-phenyl)amino)-2-propanol,2,2′-[1,2-Ethanediyl-bis-(oxy-2,1-ethanediyloxy)]-bis-benzene-1,4-diamine;N,N-Bis(2-hydroxyethyl)-p-phenylinediamine, p-aminophenol derivativessuch as: 4-amino-phenol (commonly known as p-aminophenol),4-methylamino-phenol, 4-amino-3-methyl-phenol,4-amino-2-hydroxymethyl-phenol, 4-amino-2-methyl-phenol,4-amino-1-hydroxy-2-(2′-hydroxyethylaminomethyl)benzene,4-amino-2-methoxymethyl-phenol, 5-amino-2-hydroxy-benzoic acid,1-(5-amino-2-hydroxy-phenyl)-ethane-1,2-diol,4-amino-2-(2-hydroxy-ethyl)-phenol, 4-amino-3-(hydroxymethyl)phenol,4-amino-3-fluoro-phenol, 4-amino-2-(aminomethyl)-phenol,4-amino-2-fluoro-phenol, 1-hydroxy-2,4-diaminobenzene;1-(2′-hydroxyethyloxy)-2,4-diaminobenzene, and2,4-diamino-5-methylphenetol; o-phenylenediamine derivatives such as:3,4-diaminobenzoic acid and salts thereof; o-aminophenol derivativessuch as: 2-amino-phenol (commonly known as o-aminophenol),2,4-diaminophenol, 2-amino-5-methyl-phenol, 2-amino-6-methyl-phenol,N-(4-amino-3-hydroxy-phenyl)-acetamide, and 2-amino-4-methyl-phenol; andheterocyclic derivatives such as: pyrimidine-2,4,5,6-tetramine (commonlyknown as 2,4,5,6-tetraaminopyridine), 1-methyl-1H-pyrazole-4,5-diamine,2-(4,5-diamino-1H-pyrazol-1-yl)ethanol,N²,N²-dimethyl-pyridine-2,5-diamine,2-[(3-amino-6-methoxypyridin-2-yl)amino]ethanol,6-methoxy-N²-methyl-pyridine-2,3-diamine,2,5,6-triaminopyrimidin-4(1H)-one, pyridine-2,5-diamine,1-isopropyl-1H-pyrazole-4,5-diamine,1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine,1-(benzyl)-1H-pyrazole-4,5-diamine,1-(4-chlorobenzyl)-1H-pyrazole-4,5-diamine,pyrazolo[1,5-a]-pyrimidine-3,7-diamine,5,6,7-trimethylpyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride,7-methylpyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride,2,5,6,7-teramethyl-pyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride,5,7-di-tert-butylpyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride,5,7-di-trifluoromethyl-pyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride,2-methylpyrazolo[1,5-a]pyrimidin-3,7-diamine hydrochloride,4-hydroxy-2,5,6-triaminopyrimidine,1-(2′hydroxyethyl)-amino-3,4-methylene dioxybenzene, and1-hydroxyethyl-4,5-diaminopyrazole sulphate.

Preferred developers include, but are not limited to: p-phenylenediaminederivatives such as: 2-methyl-benzene-1,4-diamine; benzene-1,4-diamine;1-(2,5-diamino-phenyl)-ethanol; 2-(2,5-diamino-phenyl)-ethanol;2-thiazole-2-yl-benzene-1,4-diamine,2-(6-methyl-pyridin-2-yl)-benzene-1,4-diamine,3′-fluoro-biphenyl-2,5-diamine, 2-propenyl-2-yl-benzene-1,4-diamine,2-(methoxymethyl)benzene-1,4-diamine,N-(2-methoxyethyl)benzene-1,4-diamine;2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol;1-(2,5-diaminophenyl)ethane-1,2-diol;1-(2′-Hydroxyethyl)-2,5-diaminobenzene;1,3-Bis(N(2-Hydroxyethyl)-N-(4-amino-phenyl)amino)-2-propanol;2,2′-[1,2-Ethanediyl-bis-(oxy-2,1-ethanediyloxy)]-bis-benzene-1,4-diamine;N,N-Bis(2-hydroxyethyl)-p-phenylinediamine; and mixtures thereof;p-aminophenol derivatives such as: 4-amino-phenol, 4-methylamino-phenol,4-amino-3-methyl-phenol, 4-amino-2-methoxymethyl-phenol;1-(5-amino-2-hydroxy-phenyl)-ethane-1,2-diol;1-Hydroxy-2,4-diaminobenzene; 1-(2′-Hydroxyethyloxy)-2,4-diaminobenzene;4-Amino-2-aminomethylphenol; 2,4-Diamino-5-methylphenetol;4-Amino-1-hydroxy-2-(2′-hydroxyethylaminomethyl)benzene;1-methoxy-2-amino-4-(2′hydroxyethylamino)benzene; 5-aminosalicylic acidand salts thereof; and mixtures thereof; o-phenylenediamine derivativessuch as: 3,4-Diaminobenzoic acid and salts thereof; o-aminophenolderivatives such as: 2-amino-phenol, 2-amino-5-methyl-phenol,2-amino-6-methyl-phenol, N-(4-amino-3-hydroxy-phenyl)-acetamide;2-amino-4-methyl-phenol; and mixtures thereof; and heterocyclicderivatives such as: pyrimidine-2,4,5,6-tetramine;1-methyl-1H-pyrazole-4,5-diamine;2-(4,5-diamino-1H-pyrazol-1-yl)ethanol;1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine;1-(benzyl)-1H-pyrazole-4,5-diamine; N²,N²-dimethyl-pyridine-2,5-diamine;4-Hydroxy-2,5,6-triaminopyrimidine;1-(2′hydroxyethyl)-amino-3,4-methylene dioxybenzene; and1-Hydroxyethyl-4,5-diaminopyrazole sulphate; and mixtures thereof.

More preferred developers include: 2-methyl-benzene-1,4-diamine;benzene-1,4-diamine; 2-thiazole-2-yl-benzene-1,4-diamine,2-(6-methyl-pyridin-2-yl)-benzene-1,4-diamine,3′-fluoro-biphenyl-2,5-diamine, 2-propenyl-2-yl-benzene-1,4-diamine,2-(methoxymethyl)benzene-1,4-diamine,N,N-Bis(2-hydroxyethyl)-p-phenylenediamine; 4-amino-phenol;4-methylamino-phenol; 4-amino-3-methyl-phenol;1-Hydroxy-2,4-diaminobenzene; 2-amino-phenol; 2-amino-5-methyl-phenol;2-amino-6-methyl-phenol; 1-methyl-1H-pyrazole-4,5-diamine;1-Hydroxyethyl-4,5-diaminopyrazole sulphate;2-(4,5-diamino-1H-pyrazol-1-yl)ethanol; and mixtures thereof.

2. Auxiliary Couplers

Suitable couplers for use in the compositions described herein include,but are not limited to: phenol, resorcinol, and naphthol derivativessuch as: naphthalene-1,7-diol, benzene-1,3-diol,4-chlorobenzene-1,3-diol, naphthalen-1-ol, 2-methyl-naphthalen-1-ol,naphthalene-1,5-diol, naphthalene-2,7-diol, benzene-1,4-diol,2-methyl-benzene-1,3-diol, 7-amino-4-hydroxy-naphthalene-2-sulfonicacid, 2-isopropyl-5-methylphenol,1,2,3,4-tetrahydro-naphthalene-1,5-diol, 2-chloro-benzene-1,3-diol,4-hydroxy-naphthalene-1-sulfonic acid, benzene-1,2,3-triol,naphthalene-2,3-diol, 5-dichloro-2-methylbenzene-1,3-diol,4,6-dichlorobenzene-1,3-diol, 2,3-dihydroxy-[1,4]naphthoquinone; and1-acetoxy-2-methylnaphthalene; m-phenylenediamine derivatives such as:2,4-diaminophenol, benzene-1,3-diamine, 2-(2,4-diamino-phenoxy)-ethanol,2-[(3-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol,2-mehyl-benzene-1,3-diamine,2-[[2-(2,4-diamino-phenoxy)-ethyl]-(2-hydroxy-ethyl)-amino]-ethanol,4-{3-[(2,4-diaminophenyl)oxy]propoxy}benzene-1,3-diamine,2-(2,4-diamino-phenyl)-ethanol,2-(3-amino-4-methoxy-phenylamino)-ethanol,4-(2-amino-ethoxy)-benzene-1,3-diamine, (2,4-diamino-phenoxy)-aceticacid, 2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol,4-ethoxy-6-methyl-benzene-1,3-diamine,2-(2,4-diamino-5-methyl-phenoxy)-ethanol,4,6-dimethoxy-benzene-1,3-diamine,2-[3-(2-hydroxy-ethylamino)-2-methyl-phenylamino]-ethanol,3-(2,4-diamino-phenoxy)-propan-1-ol, N-[3-(dimethylamino)phenyl]urea,4-methoxy-6-methylbenzene-1,3-diamine,4-fluoro-6-methylbenzene-1,3-diamine,2-({3-[(2-hydroxyethyl)amino]-4,6-dimethoxyphenyl}-amino)ethanol,3-(2,4-diaminophenoxy)-propane-1,2-diol,2-[2-amino-4-(methylamino)-phenoxy]ethanol,2-[(5-amino-2-ethoxy-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol,2-[(3-aminophenyl)amino]ethanol,2,4-Diamino-5-(2′-hydroxyethyloxy)toluene; N,N-Dimethyl-3-ureidoaniline;N-(2-aminoethyl)benzene-1,3-diamine,4-{[(2,4-diamino-phenyl)oxy]methoxy}-benzene-1,3-diamine,1-methyl-2,6-bis(2-hydroxyethylamino)benzene; and2,4-dimethoxybenzene-1,3-diamine; m-aminophenols such as:3-amino-phenol, 2-(3-hydroxy-4-methyl-phenylamino)-acetamide,2-(3-hydroxy-phenylamino)-acetamide, 5-amino-2-methyl-phenol,5-(2-hydroxy-ethylamino)-2-methyl-phenol, 5-amino-2,4-dichloro-phenol,3-amino-2-methyl-phenol, 3-amino-2-chloro-6-methyl-phenol,5-amino-2-(2-hydroxy-ethoxy)-phenol,2-chloro-5-(2,2,2-trifluoro-ethylamino)-phenol,5-amino-4-chloro-2-methyl-phenol, 3-cyclopentylamino-phenol,5-[(2-hydroxyethyl)amino]-4-methoxy-2-methylphenol,5-amino-4-methoxy-2-methylphenol, 3-(dimethylamino)phenol,3-(diethylamino)phenol, 5-amino-4-fluoro-2-methylphenol,5-amino-4-ethoxy-2-methylphenol, 3-amino-2,4-dichloro-phenol,3-[(2-methoxyethyl)amino]phenol, 3-[(2-hydroxyethyl)amino]phenol,5-amino-2-ethyl-phenol, 5-amino-2-methoxyphenol,5-[(3-hydroxy-propyl)amino]-2-methylphenol,3-[(3-hydroxy-2-methylphenyl)-amino]propane-1,2-diol,3-[(2-hydroxyethyl)amino]-2-methylphenol;1-Methyl-2-hydroxy-4-(2′-hydroxyethyl)amino-benzene;1,3-Bis-(2,4-Diaminophenoxy)propane;1-Hydroxy-2-methyl-5-amino-6-chlorobenzene; and heterocyclic derivativessuch as: 3,4-dihydro-2H-1,4-benzoxazin-6-ol,4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one,6-methoxyquinolin-8-amine, 4-methylpyridine-2,6-diol,2,3-dihydro-1,4-benzodioxin-5-ol, 1,3-benzodioxol-5-ol,2-(1,3-benzodioxol-5-ylamino)ethanol, 3,4-dimethylpyridine-2,6-diol,5-chloropyridine-2,3-diol, 2,6-dimethoxypyridine-3,5-diamine,1,3-benzodioxol-5-amine, 2-{[3,5-diamino-6-(2-hydroxy-ethoxy)-pyridin-2-yl]oxy}-ethanol,1H-indol-4-ol, 5-amino-2,6-dimethoxypyridin-3-ol, 1H-indole-5,6-diol,1H-indol-7-ol, 1H-indol-5-ol, 1H-indol-6-ol,6-bromo-1,3-benzodioxol-5-ol,2-aminopyridin-3-ol, pyridine-2,6-diamine,3-[(3,5-diaminopyridin-2-yl)oxy]propane-1,2-diol,5-[(3,5-diaminopyridin-2-yl)oxy]pentane-1,3-diol, 1H-indole-2,3-dione,indoline-5,6-diol, 3,5-dimethoxypyridine-2,6-diamine,6-methoxypyridine-2,3-diamine; 3,4-dihydro-2H-1,4-benzoxazin-6-amine;4-hydroxy-N-methylindole, 1H-5-methylpyrazol-5-one,1-phenyl-3-methylpyrazol-5-one,2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole,2,6-dimethyl[3,2-c]-1,2,4-triazole,6-methylpyrazolo-[1,5-a]benzimidazole, 2,6-dihydroxypyridine,2,6-dihydroxy-3,4-dimethylpyridine,5-methylpyrazolo[5,1-e]-1,2,3-triazole,5-methyl-6-chloropyrazolo[5,1-e]-1,2,3,-triazole,5-phenylpyrazolo[5,1-e]-1,2,3-triazole and its addition salts,1H-2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole tosylate,7,8-dicyano-4-methylimidazolo-[3,2-a]imidazole,2,7-dimethylpyrazolo[1,5-a]pyrimidin-5-one,2,5-dimethylpyrazolo[1,5-a]pyrimidin-7-one, and2-methyl-5-methoxymethyl-pyrazolo[1,5-a]pyrimidin-7-one;6-Hydroxybenzomorpholine; and 3-Amino-2-methylamino-6-methoxypyridine;and1-Phenyl-3-methyl-5-pyrazolone-2,4-dihydro-5,2-phenyl-3H-pyrazole-3-one.

Preferred couplers include, but are not limited to: phenol, resorcinol,and naphthol derivatives such as: naphthalene-1,7-diol,benzene-1,3-diol, 4-chlorobenzene-1,3-diol, naphthalen-1-ol,2-methyl-naphthalen-1-ol, naphthalene-1,5-diol, naphthalene-2,7-diol,benzene-1,4-diol, 2-methyl-benzene-1,3-diol, and2-isopropyl-5-methylphenol; 1,2,4-Trihydroxybenzene;1-Acetoxy-2-methylnaphthalene;and mixtures thereof; m-phenylenediaminederivatives such as: benzene-1,3-diamine,2-(2,4-diamino-phenoxy)-ethanol,4-{3-[(2,4-diaminophenyl)oxy]propoxy}benzene-1,3-diamine,2-(3-amino-4-methoxy-phenylamino)-ethanol,2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol, and3-(2,4-diamino-phenoxy)-propan-1-ol;2,4-Diamino-5-(2′-hydroxyethyloxy)toluene; N,N-Dimethyl-3-ureidoaniline;2,4-Diamino-5-fluorotoluenesulfatehydrate;1-methyl-2,6-bis(2-hydroxyethylamino)benzene; and mixtures thereof;m-aminophenol derivatives such as: 3-amino-phenol,5-amino-2-methyl-phenol, 5-(2-hydroxy-ethylamino)-2-methyl-phenol, and3-amino-2-methyl-phenol;1-Methyl-2-hydroxy-4-(2′-hydroxyethyl)aminobenzene;1-Hydroxy-3-amino-2,4-dichlorobenzene;1,3-Bis-(2,4-Diaminophenoxy)propane;1-Hydroxy-2-methyl-5-amino-6-chlorobenzene;5-Amino-4-chloro-2-methylphenol; and mixtures thereof; and heterocyclicderivatives such as: 3,4-dihydro-2H-1,4-benzoxazin-6-ol,4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, 1,3-benzodioxol-5-ol,1,3-benzodioxol-5-amine, 1H-indol-4-ol, 1H-indole-5,6-diol,1H-indol-7-ol, 1H-indol-5-ol, 1H-indol-6-ol, 1H-indole-2,3-dione,pyridine-2,6-diamine, 2-aminopyridin-3-ol, 4-hydroxy-N-methylindole,1H-5-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one,2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole,2,6-dimethyl[3,2-c]-1,2,4-triazole,6-methylpyrazolo-[1,5-a]benzimidazole; 2,6-dihydroxypyridine;2,6-dihydroxy-3,4-dimethylpyridine; 6-Hydroxybenzomorpholine;2,6-Dihydroxy-3,4-dimethylpyridine; 3,5-Diamino-2,6-dimethoxypyridine;3-Amino-2-methylamino-6-methoxypyridine;1-Phenyl-3-methyl-5-pyrazolone-2,4-dihydro-5,2-phenyl-3H-pyrazole-3-one;and mixtures thereof.

More preferred couplers include: benzene-1,3-diol;4-chlorobenzene-1,3-diol; 2-methyl-benzene-1,3-diol;benzene-1,3-diamine; 3-amino-phenol; 5-amino-2-methyl-phenol;1-Methyl-2-hydroxy-4-(2′-hydroxyethyl)aminobenzene;4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one; 2-aminopyridin-3-ol;1-phenyl-3-methylpyrazol-5-one;1-Phenyl-3-methyl-5-pyrazolone-2,4-dihydro-5,2-phenyl-3H-pyrazole-3-one;and mixtures thereof.

C. Cosmetically Acceptable Medium

The compositions for dyeing keratin fibers of the present inventioncomprise a cosmetically acceptable medium for the one or more keratindyeing compounds. The cosmetically acceptable suitable may be selectedfrom water, or a mixture of water and at least one organic solvent todissolve any compounds which would not typically be sufficiently solublein water. Suitable organic solvents for use herein include, but are notlimited to, C1 to C4 lower alkanols (e.g., ethanol, propanol,isopropanol), aromatic alcohols (e.g., benzyl alcohol andphenoxyethanol); polyols and polyol ethers (e.g., carbitols,2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether,diethylene glycol monoethyl ether, monomethyl ether, hexylene glycol,glycerol, ethoxy glycol), and propylene carbonate. When present, organicsolvents are typically present in an amount ranging from about 1% toabout 30% by weight of the composition. Preferred solvents are water,ethanol, propanol, isopropanol, glycerol, 1,2-propylene glycol, hexyleneglycol, ethoxy diglycol, and mixtures thereof.

D. Additional Keratin Dyeing Composition Components

The inventive compositions for dyeing keratin fibers comprise at leastone boronic acid or boronic ester keratin dyeing compound, at least oneadditional keratin dyeing compound, and a cosmetically acceptablemedium. The inventive compositions may further comprise additionalcomponents known, conventionally used, or otherwise effective for use inoxidative dye compositions, including but limited to: direct dyes;oxidizing agents; thickeners; chelants; pH modifiers and bufferingagents; carbonate ion sources and radical scavenger systems; anionic,cationic, nonionic, amphoteric or zwitterionic surfactants, or mixturesthereof; anionic, cationic, nonionic, amphoteric or zwitterionicpolymers, or mixtures thereof; fragrances; buffers; dispersing agents;peroxide stabilizing agents; natural ingredients, e.g. proteins andprotein derivatives, and plant materials (e.g. aloe, chamomile and hennaextracts); silicones (volatile or non-volatile, modified ornon-modified), film-forming agents, ceramides, preserving agents; andopacifiers.

Some adjuvants referred to above, but not specifically described below,which are suitable are listed in the International Cosmetics IngredientDictionary and Handbook, (8^(th) ed.; The Cosmetics, Toiletry, andFragrance Association). Particularly, vol. 2, sections 3 (ChemicalClasses) and 4 (Functions) are useful in identifying specific adjuvantsto achieve a particular purpose or multipurpose.

1. Direct Dyes

The compositions of the present invention may also comprise compatibledirect dyes, in an amount sufficient to provide additional coloring,particularly with regard to intensity. Typically, such an amount willrange from 0.05% to 4%, by weight, of the composition. Suitable directdyes include, but are not limited to: Acid Yellow 1, Acid Orange 3,Disperse Red 17, Basic Brown 17, Acid Black 52, Acid Black 1, DisperseViolet 4,4-Nitro-o-Phenylenediamine, 2-Nitro-p-Phenylenediamine,Picramic Acid, HC Red No. 13,1,4-Bis-(2′-Hydroxyethyl)-amino-2-nitrobenzene, HC Yellow No. 5, HC RedNo. 7, HC Blue No. 2, HC Yellow No. 4, HC Yellow No. 2, HC Orange No. 1,HC Red No. 1, 2-Chloro-5-nitro-N-Hydroxyethyl-p-phenylenediamine, HC RedNo. 3, 4-Amino-3-nitrophenol, 2-Hydroxyethylamino-5-nitroanisole,3-nitro-p-Hydroxyethylaminophenol, 2-amino-3-nitrophenol,6-nitro-o-toluidine, 3-methylamino-4-nitrophenoxyethanol,2-nitro-5-glycerymethylanaline, HC Yellow No. 11, HC Violet No. 1, HCOrange No. 2, HC Orange No. 3, HC Yellow No. 9, 4-NitrophenylAminoethylurea, HC Red No. 10, HC Red No. 11, 2-Hydroxyethyl picramicacid, HC Blue No. 12, HC Yellow No. 6, Hydroxyethyl-2-nitro-p-toluidine,HC Yellow No. 12, HC Blue No. 10, HC Yellow No. 7, HC Yellow No. 10, HCBlue No. 9, N-ethyl-3-nitro PABA,4-amino-2-nitrophenyl-amine-2′-carboxylic acid,2-chloro-6-ethylamino-4-nitrophenol, 6-Nitro-2,5-pyridinediamine, HCViolet No. 2, 2-amino-6-chloro-4-nitrophenol,4-hydroxypropylamino-3-nitrophenol, HC Yellow No. 13,1,2,3,4-Tetrahydro-6-nitrochinoxalin, HC Red No. 14, HC Yellow No. 15,HC Yellow No. 14, 3-Amino-6-methylamino-2-nitropyridine,2,6-diamino-3-((pyridine-3-yl)azo)pyridine, Basic Red No. 118, BasicOrange No. 69, N-(2-nitro-4-aminophenyl)-allylamine,4-[(4-Amino-3-methylphenyl)(4-Imino-3-methyl-2,5-Cyclohexadien-1-ylidene)Methyl]-2-Methyl-benzeneamine-Hydrochloride,1H-Imidazolium,2-[[4-(dimethyl-amino)phenyl]azo]-1,3-dimethylchloride,Pyridinium, 1-methyl-4-[(methylphenyl-hydrazono)methyl]-, methylsulfate, 1H-Imidazolium, 2-[(4-aminophenyl)azo]-1,3-dimethyl, chloride,Basic Red 22, Basic Red 76, Basic Brown 16, Basic Yellow 57,7-(2′,4′-Dimethyl-5′-sulfophenylazo)-5-sulfo-8-hydroxynaphthalene, AcidOrange 7, Acid Red 33,1-(3′-Nitro-5′-sulfo-6′-oxophenylazo)-oxo-naphthalene chromium complex,Acid Yellow 23, Acid Blue 9, Basic Violet 14, Basic Blue 7, Basic Blue26, Sodium salt of mixture of mono- & disulfonic acids (mainly thelatter) of quinophthlanone or 2-quinolylindandione, Basic Red 2, BasicBlue 99, Disperse Red 15, Acid Violet 43, Disperse Violet 1, Acid Blue62, Pigment Blue 15, Acid Black 132, Basic Yellow 29, Disperse Black 9,1-(N-Methylmorpholinium-propylamino)-4-hydroxy-anthraquinonemethylsulfate, HC Blue No. 8, HC Red No. 8, HC Green No. 1, HC Red No.9, 2-Hydroxy-1,4-naphthoquinone, Acid Blue 199, Acid Blue 25, Acid Red4, Henna Red, Indigo, Cochenille, HC Blue 14, Disperse Blue 23, DisperseBlue 3, Violet 2, Disperse Blue 377, Basic Red 51, Basic Orange 31,Basic Yellow 87, and mixtures thereof. Preferred direct dyes include butare not limited to: Disperse Black 9, HC Yellow 2, HC Yellow 4, HCYellow 15, 4-nitro-o-phenylenediamine, 2-amino-6-chloro-4-nitrophenol,HC Red 3, Disperse Violet 1, HC Blue 2, Disperse Blue 3, Disperse Blue377, Basic Red 51, Basic Orange 31, Basic Yellow 87, and mixturesthereof.

2. Oxidizing Agent

The compositions of the present invention may further comprise anoxidizing agent, present in an amount sufficient to bleach melaninpigment in hair and/or to cause formation of dye chromophores fromoxidative dye precursors (including developers and/or couplers whenpresent). Typically, such an amount ranges from 1% to 20%, preferablyfrom 3% to 15%, more preferably from 6% to 12%, by weight, of thedeveloper composition. Inorganic peroxygen materials capable of yieldinghydrogen peroxide in an aqueous medium are preferred, and include, butare not limited to: hydrogen peroxide; inorganic alkali metal peroxides(e.g., sodium periodate and sodium peroxide); organic peroxides (e.g.,urea peroxide, melamine peroxide); inorganic perhydrate salt bleachingcompounds (e.g., alkali metal salts of perborates, percarbonates,perphosphates, persilicates, and persulphates, preferably sodium saltsthereof), which may be incorporated as monohydrates, tetrahydrates,etc.; alkali metal bromates; enzymes such as laccases and peroxidases;and mixtures thereof. A two electron oxidizing agent, such as alkaliferricyanide, may be used. Preferred is hydrogen peroxide.

3. Thickeners

The compositions of the present invention may additionally comprise athickener in an amount sufficient to provide the composition with aviscosity so that it can be readily applied to the hair without undulydripping off the hair and causing mess. Typically, such an amount willbe at least 0.1%, preferably at least 0.5%, more preferably, at least1%, by weight, of the composition.

Preferred for use herein are salt tolerant thickeners, including but notlimited to: xanthan, guar, hydroxypropyl guar, scleroglucan, methylcellulose, ethyl cellulose (available as AQUACOTE(™)), hydroxyethylcellulose (NATROSOL(™)), carboxymethyl cellulose, hydroxypropylmethylcellulose, microcrystalline cellulose, hydroxybutylmethyl cellulose,hydroxypropyl cellulose (available as KLUCEL(™)), hydroxyethyl ethylcellulose, cetyl hydroxyethyl cellulose (available as NATROSOL(™) Plus330), N-vinylpyrollidone (available as POVIDONE(™)), Acrylates/Ceteth-20Itaconate Copolymer (available as STRUCTURE (™) 3001), hydroxypropylstarch phosphate (available as STRUCTURE(™) ZEA), polyethoxylatedurethanes or polycarbamyl polyglycol ester (e.g. PEG-150/Decyl/SMDIcopolymer (available as ACULYN(™) 44), PEG-150/Stearyl/SMDI copolymeravailable as ACULYN(™) 46), trihydroxystearin (available as THIXCIN(™)),acrylates copolymer (e.g., available as ACULYN(™) 33) or hydrophobicallymodified acrylate copolymers (e.g., Acrylates/Steareth-20 MethacrylateCopolymer (available as ACULYN(™) 22), non-ionic amphiphilic polymerscomprising at least one fatty chain and at least one hydrophilic unitselected from polyether urethanes comprising at least one fatty chain,and blends of Ceteth-10 phosphate, Di-cetyl phosphate and Cetearylalcohol (available as CRODAFOS(™) CES).

4. Chelants

The compositions of the present invention may also comprise chelants inan amount sufficient to reduce the amount of metals available tointeract with formulation components, particularly oxidizing agents,more particularly peroxides. Typically such an amount will range from atleast 0.25%, preferably at least 0.5%, by weight, of the composition.Suitable chelants for use herein include but are not limited to:diamine-N,N′-dipolyacid, monoamine monoamide-N,N′-dipolyacid, andN,N′-bis(2-hydroxybenzyl)ethylenediamine-N,N′-diacetic acid chelants(preferably ethylenediaminedisuccinic acid (“EDDS”)), carboxylic acids(preferably aminocarboxylic acids), phosphonic acids (preferablyaminophosphonic acids) and polyphosphoric acids (in particular straightpolyphosphoric acids), their salts and derivatives.

5. pH Modifiers and Buffering Agents

The compositions of the present invention may further comprise a pHmodifier and/or buffering agent in an amount that is sufficientlyeffective to adjust the pH of the composition to fall within a rangefrom 3 to 13, preferably from 8 to 12, more preferably from 9 to 11.Suitable pH modifiers and/or buffering agents for use herein include,but are not limited to: ammonia, alkanolamides such as monoethanolamine,diethanolamine, triethanolamine, monopropanolamine, dipropanolamine,tripropanolamine, tripropanolamine, 2-amino-2-methyl-1-propanol, and2-amino-2-hydroxymethyl-1,3,-propandiol and guanidium salts, alkalimetal and ammonium hydroxides and carbonates, preferably sodiumhydroxide and ammonium carbonate, and acidulents such as inorganic andinorganic acids, e.g., phosphoric acid, acetic acid, ascorbic acid,citric acid or tartaric acid, hydrochloric acid, and mixtures thereof.

6. Carbonate Ion Source and Radical Scavenger System

The compositions of the present invention may also comprise a systemcomprising a source of carbonate ions, carbamate ions, and/orhydrocarbonate ions, and a radical scavenger, in a sufficient amount toreduce damage to the hair during the coloring process. Typically, suchan amount will range from 0.1% to 15%, preferably 0.1% to 10%, morepreferably 1% to 7%, by weight of the composition, of the carbonate ion,and from 0.1% to 10%, preferably from 1% to 7%, by weight of thecomposition, of radical scavenger. Preferably, the radical scavenger ispresent at an amount such that the ratio of radical scavenger tocarbonate ion is from 1:1 to 1:4. The radical scavenger is preferablyselected such that it is not an identical species as the alkalizingagent.

Suitable sources for the ions include but are not limited to: sodiumcarbonate, sodium hydrogen carbonate, potassium carbonate, potassiumhydrogen carbonate, guanidine carbonate, guanidine hydrogen carbonate,lithium carbonate, calcium carbonate, magnesium carbonate, bariumcarbonate, ammonium carbonate, ammonium hydrogen carbonate and mixturesthereof. Preferred sources of carbonate ions are sodium hydrogencarbonate and potassium hydrogen carbonate. Also preferred are ammoniumcarbonate, and ammonium hydrogen carbonate.

The radical scavenger is a species that can react with a carbonateradical to convert the carbonate radical by a series of fast reactionsto a less reactive species. Preferably, when the radical scavengercomprises an N atom, it has a pKa>7 to prevent the protonation of thenitrogen. Preferred radical scavengers may be selected from the classesof alkanolamines, amino sugars, amino acids and mixtures thereof, andmay include, but are not limited to: monoethanolamine,3-amino-1-propanol, 4-amino-1-butanol,5-amino-1-pentanol,1-amino-2-propanol, 1-amino-2-butanol, 1-amino-2-pentanol,1-amino-3-pentanol, 1-amino-4-pentanol, 3-amino-2-methylpropan-1-ol,1-amino-2-methylpropan-2-ol, 3-aminopropane-1,2-diol, glucosamine,N-acetylglucosamine, glycine, arginine, lysine, proline, glutamine,histidine, serine, tryptophan and potassium, sodium and ammonium saltsof the above and mixtures thereof. Other preferred radical scavengercompounds include benzylamine, glutamic acid, imidazole,di-tert-butylhydroxytoluene, hydroquinone, catechol, and mixturesthereof.

II. Methods of Manufacture

The compositions of this invention may be obtained using conventionalmethods. A general description of how to make the boronic acid andboronic ester compounds is provided above, along with specific examplesof such compounds. The compositions of this invention also may beobtained using conventional methods. The keratin dyeing compositions maybe formed as solutions, preferably as aqueous or aqueous-alcoholsolutions. The hair dye product compositions may preferably be formed asthick liquids, creams, gels, or emulsions whose composition is a mixtureof the dye compound and other dye ingredients with conventional cosmeticadditive ingredients suitable for the particular preparation.

III. Methods of Use

The inventive keratin dyeing compositions may be used by admixing themwith a suitable oxidizing agent, which reacts with the oxidative dyeprecursors to develop the hair dye product composition. The oxidizingagent is usually provided in an aqueous composition, which normally isprovided as a separate component of the finished keratin dyeing productsystem and present in a separate container. Upon mixing the keratindyeing composition, the adjuvants are provided in the hair dyecomposition as it is applied to the hair to achieve desired productattributes, e.g., pH, viscosity, rheology, etc.

The keratin dyeing composition as it is applied to the hair, can beweakly acidic, neutral or alkaline according to their composition,typically having a pH from 6 to 11, preferably from 7 to 10, morepreferably from 8 to 10. The pH of the developer composition istypically acidic, and generally the pH is from 2.5 to 6.5, preferablyfrom 3 to 5. The pH of the hair compositions may be adjusted using a pHmodifier as mentioned above.

In order to use the keratin dyeing composition, the above-describedcompositions are mixed immediately prior to use and a sufficient amountof the mixture is applied to the hair, according to the hair abundance,generally from 60 to 200 grams. Upon such preparation the hair dyecomposition is applied to the hair to be dyed and remains in contactwith the hair for an amount of time effective to dye the hair.Typically, the hair dye composition is allowed to act on the hair for 2to 60, preferably 15 to 45, more preferably, 30 minutes, at atemperature ranging from 15° C. to 50° C. Thereafter, the hair is rinsedwith water, to remove the hair dye composition and dried. If necessary,the hair is washed with a shampoo and rinsed, e.g., with water or aweakly acidic solution, such as a citric acid or tartaric acid solution,and dried. Optionally, a separate conditioning product may also beprovided.

Together, components of the keratin dyeing composition form a system fordyeing hair. This system may be provided as a kit comprising in a singlepackage separate containers of the keratin dyeing composition componentsor other hair treatment product, and instructions for use.

Non-Limiting Examples

The following are non-limiting examples of the compositions of thepresent invention. The examples are given solely for the purpose ofillustration and are not to be construed as limitations of the presentinvention, as many variations thereof are possible without departingfrom the spirit and scope of the invention, which would be recognized byone of ordinary skill in the art. In the examples, all concentrationsare listed as weight percent, unless otherwise specified.

The following compositions shown in Tables 1 and 3 can be used foroxidatively dyeing hair. The dyeing composition is mixed with an equalweight of a 20-volume hydrogen peroxide solution (i.e., 6% by weight).The resulting mixture is applied to bleached yak hair and permitted toremain in contact with the hair for 30 minutes at 40° C. This dyed hairis then shampooed and rinsed with water and dried. The CIE L*a*b*, C*,and h values are measured by using Minolta Spectrophotometer CM-3700d(as shown in Tables 2 and 4, respectively, for the compositions ofTables 1 and 3).

TABLE 1 Dye Base Ingredients Ingredient Wt % Dyes 0.025 M Sodium sulfite0.1 Ascorbic Acid 0.4 Ethanol 10.0 Ammonium carbonate 7.0 EDTA 0.3Sodium glycinate 3.02 Sodium lauryl ether sulfate 10.0 DeionizedWater/KOH to pH = 9 Q.S to 100

TABLE 2 The CIE L*a*b*C*h values obtained by coupling one of3-hydroxyphenylboronic acid,3-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenol, and1-naphthaleneboronic acid with various developers. Developer Coupler L*a* b* C* h

33.41 4.23 14.77 15.36 74.00

44.65 2.50 20.96 21.11 83.20

59.75 1.93 14.31 14.44 82.32

53.75 24.53 10.34 26.62 22.86

33.49 4.19 15.08 15.65 74.49

44.73 1.72 20.25 20.32 85.15

60.23 2.52 16.98 17.17 81.57

50.49 19.14 7.00 20.38 20.09

27.30 9.80 −14.53 17.53 303.99

43.12 27.85 8.02 28.98 16.06

28.08 37.27 −11.08 38.88 343.44

30.79 2.14 −29.85 29.93 274.09

34.48 27.28 11.54 29.63 22.93

20.46 8.81 −8.65 12.34 315.52

24.83 32.63 −6.82 33.33 348.19

24.07 2.07 −24.04 24.13 274.91

60.09 4.55 17.62 18.20 75.53

34.55 5.71 8.65 10.37 56.57

39.22 33.86 −2.55 33.95 355.70

45.50 −3.13 −2.05 3.74 213.21 Untreated hair 71.19 −0.39 3.43 3.45 96.48

TABLE 3 Dye Base Ingredients Ingredient Wt % Dyes 0.025 M Sodium sulfite0.1 Ascorbic Acid 0.4 Ethanol 10.0 EDTA 0.3 Ammoniun hydroxide 9.0Sodium lauryl ether sulfate 10.0 Deionized Water Q.S to 100

TABLE 4 The CIE L*a*b*C*h values obtained by coupling one of3-hydroxyphenylboronic acid,3-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenol, and1-naphthaleneboronic acid with various developers. Developer Coupler L*a* b* C* h

34.08 4.73 14.25 15.01 71.63

41.60 4.33 17.26 17.79 75.91

62.99 1.59 19.42 19.49 85.32

47.46 26.50 6.50 27.29 13.78

34.15 4.90 13.63 14.49 70.22

42.54 4.43 17.12 17.68 75.48

64.03 2.46 20.64 20.79 83.20

48.02 26.76 6.49 27.54 13.64

20.04 8.29 −11.80 14.42 305.11

21.08 27.05 −4.85 27.48 349.82

22.39 8.38 −29.83 30.98 285.69 Untreated hair 71.19 −0.39 3.43 3.4596.48

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm”.

All documents cited in the Detailed Description of the Invention are, inrelevant part, incorporated herein by reference; the citation of anydocument is not to be construed as an admission that it is prior artwith respect to the present invention. To the extent that any meaning ordefinition of a term in this written document conflicts with any meaningor definition of the term in a document incorporated by reference, themeaning or definition assigned to the term in this written documentshall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

1. A composition for dyeing keratin fibers, said composition comprising:(a) at least one keratin dyeing compound selected from aromatic systemswhich comprise at least one boronic acid or boronic ester moiety andwhich are capable of forming upon oxidation a nucleophile or anelectrophile, wherein said aromatic system which comprises at least oneboronic acid or boronic ester moiety and which is capable of formingupon oxidation a nucleophile or an electrophile is selected from acompound according to one of the following formulas I to XV:

wherein R1, R2, R3, R4, R7, R8, R9, R10, R11, R12, and R13 each areindependently selected from the group consisting of a hydrogen atom; ahalogen atom; an amino radical, a hydroxyl radical; a cyano radical; aC₁-C₄ alkyl radical; a trifluoromethyl radical, an alkylamino radical; ahydroxyalkylamino radical; an acetylamido radical; a carboxyl radical;an alkoxy radical; an alkoxyalkyl radical; a carbamoyl radical; analkylcarbamoylradical; a hydroxyalkylcarbamoyl radical; an amidoradical; an alkylamido radical; an alkylcarbonyl radical; analkoxycarbonyl radical; an aryloxy radical; an acyloxy radical; analkylthio radical; an arylthio radical; a heteroarylthio radical; aheteroaryloxy radical; a 5- or 6-membered heterocycle having at leastone heteroatom selected from nitrogen, oxygen, or sulfur and beingoptionally substituted; an aryl radical which is optionally substituted;a sulfonyl radical; a sulfinyl radical; a phosphonyl radical; asulfamoyl radical; a siloxy radical; an acyloxy radical; a carbamoyloxyradical; a sulphonamide radical; an imide radical; a ureido radical; asulfamoylamino radical; an alkoxycarbonylamino radical; anaryloxycarbonylamino radical; an aryloxycarbonyl radical; and abenzenesulfonamido radical; wherein R is selected group consisting ofhydrogen, COR 1, and C-linked monovalent substituents selected from thegroup consisting of: (i) substituted or unsubstituted, straight orbranched, alkyl, mono- or poly-unsaturated alkyl, heteroalkyl,aliphatic, heteroaliphatic, or heteroolefinic systems, (ii) substitutedor unsubstituted, mono- or poly-cyclic aliphatic, aryl, or heterocyclicsystems, and (iii) substituted or unsubstituted, mono-, poly-hydroxy or-fluoro alkyl systems; wherein said systems of (i), (ii) and (iii)comprise from about 1 to about 10 carbon atoms and from about 0 to about5 heteroatoms selected from the group consisting of O, S, N, P, and Si;wherein R5 and R6 each are independently selected from the groupconsisting of hydrogen and lower alkyl groups which can be joinedtogether as a straight or branched alkylene chain forming a five orsix-membered ring or an aromatic ring; wherein X is selected from thegroup consisting of hydroxyl, B(OR5)OR6, and NA1A2; wherein Y and Z eachare independently selected from the group consisting of hydroxyl andB(OR5)OR6, provided that at least one of which is B(OR5)OR6; and whereinA¹ and A² are monovalent and are independently selected from the groupconsisting of hydrogen; substituted or unsubstituted, straight orbranched, alkyl, mono- or poly-unsaturated alkyl, heteroalkyl,aliphatic, heteroaliphatic, or heteroolefinic systems; substituted orunsubstituted, mono- or poly-cyclic aliphatic, aryl, or heterocyclicsystems; and substituted or unsubstituted, mono-, poly-, per-fluoroalkyl systems; or A¹ and A² together with a nitrogen atom to which theyare bound form a ring; wherein all of said systems comprise from about 1to about 10 carbon atoms and from about 0 to about 5 heteroatomsselected from the group consisting of O, S, N, P, and Si; (b) at leastone additional keratin dyeing compound selected from the groupconsisting of auxiliary developers and auxiliary couplers; and (c) acosmetically suitable medium.
 2. A composition according to claim 1,wherein said aromatic system which comprises at least one boronic acidor boronic ester moiety and which is capable of forming upon oxidation anucleophile or an electrophile is selected from the group consisting of3-hydroxyphenylboronic acid, 3-hydroxy-2-methylphenylboronic acid,2-chloro-5-hydroxyphenylboronic acid,6-chloro-3-hydroxy-2-methylphenylboronic acid,3-hydroxy-6-methoxy-2-methyiphenylboronic acid,3-hydroxy-2,4-dimethylphenylboronic acid, 2-ethyl-3-hydroxyphenylboronicacid, 3-hydroxy-2-(2-hydroxyethyl)phenylboronic acid,2-(2,2,2-trifluoroethyl)-3-hydroxyphenylboronic acid,2-(cyanomethyl)-3-hydroxyphenylboronic acid,3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol,2-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol,4-chloro-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol,4-chloro-2-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol,4-methoxy-2-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol,2,6-dimethyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol,2-ethyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol,2-(2-hydroxyethyl)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol,3-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)phenol,2-methyl-3-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)phenol,3-(benzo[d][1,3,2]dioxaborol-2-yl)phenol,3-(benzo[d][1,3,2]dioxaborol-2-yl)-2-methylphenol,3-(1,3,2-dioxaborolan-2-yl)phenol,3-(1,3,2-dioxaborolan-2-yl)-2-methylphenol, 3-aminophenylboronic acid,3-amino-2-methylphenylboronic acid, 3-(methylamino)phenylboronic acid,3-(2-hydroxyethylamino)phenylboronic acid,3-[bis(2-hydroxyethyl)amino]phenylboronic acid,3-morpholinophenylboronic acid, 3-(pyrrolidin-1-yl)phenylboronic acid,3-amino-4-chlorophenylboronic acid, 5-amino-2,4-dichlorophenylboronicacid, 5-amino-2-methoxyphenylboronic acid,3-amino-4-methoxyphenylboronic acid,3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzenamine,3-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)benzenamine,3(1,3,2-dioxaborolan-2yl)benzenamine, and3-(benzo[d][1,3,2]dioxaborol-2-yl)benzenamine.
 3. A compositionaccording to claim 1, wherein said aromatic system which comprises atleast one boronic acid or boronic ester moiety and which is capable offorming upon oxidation a nucleophile or an electrophile is selected fromthe group consisting of 2-aminophenylboronic acid,2-amino-5-methylphenylboronic acid, 2-amino-5-ethylphenylboronic acid,2-amino-4-chlorophenylboronic acid, 2-amino-4-methoxyphenylboronic acid,2-(2-hydroxyethylamino)phenylboronic acid,2-[bis(2-hydroxyethyl)amino]phenylboronic acid,2-morpholinophenylboronic acid, 2-(pyrrolidin-1-yl)phenylboronic acid,2-(methylamino)phenylboronic acid,2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzenamine,4-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzenamine,2-(1,3,2-dioxaborolan-2-yl)benzenamine,2-(benzo[d][1,3,2]dioxaborol-2-yl)benzenamine, and 2-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)benzenamine.
 4. A composition according to claim 1,wherein said aromatic system which comprises at least one boronic acidor boronic ester moiety and which is capable of forming upon oxidation anucleophile or an electrophile is selected from the group consisting of3,4-dihydro-2H-benzo [b][1,4]oxazin-6-yl-6-boronic acid,3,4-dihydro-7-methyl-2H-benzo[b][1,4]oxazin-6-yl-6-boronic acid,7-ethyl-3,4-dihydro-2H-benzo [b][1,4]oxazin-6-yl-6-boronic acid,3,4-dihydro-7-methoxy-2H-benzo[b][1,4]oxazin-6-yl-6-boronic acid,6-(1,3,2-dioxaborolan-2-yl)-3,4-dihydro-2H-benzo[b][1,4]oxazine,6-(benzo[d][1,3,2]dioxaborol-2-yl)-3,4-dihydro-2H-benzo[b][1,4]oxazine,and3,4-dihydro-6-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-2H-benzo[b][1,4]oxazine.5. A composition according to claim 1, wherein said aromatic systemwhich comprises at least one boronic acid or boronic ester moiety andwhich is capable of forming upon oxidation a nucleophile or anelectrophile is selected from the group consisting ofnaphthalen-1-yl-1-boronic acid, 2-methylnaphthalen-1-yl-1-boronic acid,2-ethylnaphthalen-1-yl-1-boronic acid, 4-chloronaphthalen-1-yl-1-boronicacid, 4-methoxynaphthalen-1-yl-1-boronic acid,4,4,5,5-tetramethyl-2-(naphthalen-4-yl)-1,3,2-dioxaborolane,4,4,5,5-tetramethyl-2-(2-methylnaphthalen-1-yl)-1,3,2-dioxaborolane,2-(naphthalen-4-yl)-1,3,2-dioxaborolane,2-(naphthalen-4-yl)benzo[d][1,3,2]dioxaborole,5,5-dimethyl-2-(naphthalen-4-yl)-,3,2-dioxaborinane,7-methylnaphthalen-1-yl-1-boronic acid,6-methylnaphthalen-1-yl-1-boronic acid,8-methylnaphthalen-1-yl-1-boronic acid,2-(2,2,2-trifluoroethyl)naphthalen-1-yl-1-boronic acid, and2-(2-hydroxyethyl)naphthalen-1-yl-1-boronic acid.
 6. A compositionaccording to claim 1, wherein said aromatic system which comprises atleast one boronic acid or boronic ester moiety and which is capable offorming upon oxidation a nucleophile or an electrophile is selected fromthe group consisting of 1H-indol-4-yl-4-boronic acid,7-chloro-1H-indol-4-yl-4-boronic acid, 7-methoxy-1H-indol-4-yl-4-boronicacid, 2-methyl-1H-indol-4-yl-4-boronic acid,2,3-dimethyl-1H-indol-4-yl-4-boronic acid,5-methyl-1H-indol-4-yl-4-boronic acid, 1-methyl-1H-indol-4-yl-4-boronicacid, 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole,4-(1,3,2-dioxaborolan-2-yl)-1H-indole,4-(benzo[d][1,3,2]dioxaborol-2-yl)-1H-indole, and4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-1H-indole.
 7. A compositionaccording to claim 1, wherein said aromatic system which comprises atleast one boronic acid or boronic ester moiety and which is capable offorming upon oxidation a nucleophile or an electrophile is selected fromthe group consisting of 1H-indol-6-yl-6-boronic acid,2-methyl-1H-indol-6-yl-6-boronic acid,2,3-dimethyl-1H-indol-6-yl-6-boronic acid,7-methyl-1H-indol-6-yl-6-boronic acid, 1-methyl-1H-indol-6-yl-6-boronicacid, 5-chloro-1H-indol-6-yl-6-boronic acid,5-methoxy-1H-indol-6-yl-6-boronic acid,6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole,6-(1,3,2-dioxaborolan-2-yl)-1H-indole,6-(benzo[d][1,3,2]dioxaborol-2-yl)-1H-indole, and6-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-1H-indole.
 8. A compositionaccording to claim 1, wherein said aromatic system which comprises atleast one boronic acid or boronic ester moiety and which is capable offorming upon oxidation a nucleophile or an electrophile is selected fromthe group consisting of 5-hydroxy-1H-indol-6-yl-6-boronic acid,6-hydroxy-1H-indol-5-yl-5-boronic acid,5-hydroxy-2-methyl-1H-indol-6-yl-6-boronic acid,6-hydroxy-2-methyl-1H-indol-5-yl-5-boronic acid,5-hydroxy-2,3-dimethyl-1H-indol-6-yl-6-boronic acid,6-hydroxy-2,3-dimethyl-1H-indol-5-yl-5-boronic acid,5-hydroxy-1-methyl-1H-indol -6-yl-6-boronic acid,6-hydroxy-1-methyl-1H-indol-5-yl-5-boronic acid,5-hydroxy-1-(2-hydroxyethyl)-1H-indol-6-yl-6-boronic acid,6-hydroxy-1-(2-hydroxyethyl)-1H-indol-5-yl-5-boronic acid,6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indol-5-ol,5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indol-6-ol,6-(1,3,2-dioxaboroian-2-yl)-1H-indol-5-ol,5-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-1H-indol-6-ol,2-methyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaboroian-2-yl)-1H-indol-5-ol,and2-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indol-6-ol.9. A composition according to claim 1, wherein said aromatic systemwhich comprises at least one boronic acid or boronic ester moiety andwhich is capable of forming upon oxidation a nucleophile or anelectrophile is selected from the group consisting of1-ethyl-3-(methylamino)-1H-pyrazol-5-yl-5-boronic acid,1-(2-hydroxyethyl)-3-(methylamino)-1H-pyrazol-5-yl-5-boronic acid,3-acetamido-1-(2-hydroxyethyl)-1H-pyrazol-5-yl-5-boronic acid,3-(2-hydroxyethylamino)-1-(2-hydroxyethyl)-1H-pyrazol-5-yl-5-boronicacid, 1-methyl-3-(methylamino)-1H-pyrazol-5-yl-5-boronic acid,5-(1,3,2-dioxaborolan-2-yl)-N,1-dimethyl-1H-pyrazol-3-amine,2-(3-(ethylamino)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazol-1-yl)ethanol,N-(1-(2-hydroxyethyl)-5-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-1H-pyrazol-3-yl)acetamide,3-amino-1-phenyl-1H-pyrazol-5-yl-5-boronic acid, andN-(5-(benzo[d][1,3,2]dioxaborol-2-yl)-1-(2-hydroxyethyl)-1H-pyrazol-3-yl)acetamide.10. A composition according to claim 1, wherein said aromatic systemwhich comprises at least one boronic acid or boronic ester moiety andwhich is capable of forming upon oxidation a nucleophile or anelectrophile is selected from the group consisting of4-amino-1-methyl-1H-pyrazol-5-yl-5-boronic acid,4-amino-1-ethyl-1H-pyrazol-5-yl-5-boronic acid,4-amino-1-(2-hydroxyethyl)-1H-pyrazol-5-yl-5-boronic acid,4-amino-1-(2-hydroxyethyl)-3-methyl-1H-pyrazol-5-yl-5-boronic acid,4-amino-1-benzyl-1H-pyrazol-5-yl-5-boronic acid,4-amino-1-isopropyl-1H-pyrazol-5-yl-5-boronic acid,5-(1,3,2-dioxaborolan-2-yl)-1-methyl-1H-pyrazol-4-amine,5-(1,3,2-dioxaborolan-2-yl)-1-ethyl-1H-pyrazol-4-amine,2-(4-amino-5-(1,3,2-dioxaborolan-2-yl)-1H-pyrazol-1-yl)ethanol,2-(4-amino-5-(1,3,2-dioxaborolan-2-yl)-3-methyl-1H-pyrazol-1-yl)ethanol,1-benzyl-5-(1,3,2-dioxaborolan-2-yl)-1H-pyrazol-4-amine,5-(1,3,2-dioxaborolan-2-yl)-1-isopropyl-1H-pyrazol-4-amine,1-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazol-4-amine,1-ethyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazol-4-amine,2-(4-amino-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazol-1-yl)ethanol,2-(4-amino-5-(1,3,2-dioxaborolan-2-yl)-3-methyl-1H-pyrazol-1-yl)ethanol,1-methyl-5-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-1H-pyrazol-4-amine,1-ethyl-5-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-1H-pyrazol-4-amine,2-(4-amino-5-(5,5-dimethyl-,1,3,2-dioxaborinan-2-yl)-1H-pyrazol-1-yl)ethanol,2-(4-amino-3-methyl-5-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-1H-pyrazol-1-yl)ethanol,1-benzyl-5-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-1H-pyrazol-4-amine,and1-isopropyl-5-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-1H-pyrazol-4-amine.11. A composition according to claim 1, wherein said aromatic systemwhich comprises at least one boronic acid or boronic ester moiety andwhich is capable of forming upon oxidation a nucleophile or anelectrophile is selected from the group consisting of4-aminophenylboronic acid, 4-amino-3-methyiphenylboronic acid,4-amino-3-ethylphenylboronic acid, 4-(methylamino)phenylboronic acid,4-(2-hydroxyethylamino)phenylboronic acid, 4-amino-3-chlorophenylboronicacid, 4-amino-3-methoxyphenylboronic acid,4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzenamine,2-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzenamine,4-(1,3,2-dioxaborolan-2-yl)benzenamine,4-(benzo[d][1,3,2]dioxaborol-2-yl)benzenamine, and 4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)benzenamine.
 12. A compositionaccording to claim 1, wherein said aromatic system which comprises atleast one boronic acid or boronic ester moiety and which is capable offorming upon oxidation a nucleophile or an electrophile is selected fromthe group consisting of 3-aminopyridin-2-yl-2-boronic acid,3-(methylamino)pyridin-2-yl-2-boronic acid,3-amino-5-chloropyridin-2-yl-2-boronic acid,3-amino-5-methoxypyridin-2-yl-2-boronic acid,3-(2-hydroxyethylamino)pyridin-2-yl-2-boronic acid,3-[bis(2-hydroxyethyl)amino]pyridin-2-yl-2-boronic acid,3-morpholinopyridin-2-yl-2-boronic acid,3-(pyrrolidin-1-yl)pyridin-2-yl-2-boronic acid,2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-3-amine,5-chloro-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-3-amine,5-methoxy-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-3-amine,N-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-3-amine,2-(1,3,2-dioxaborolan-2-yl)pyridin-3-amine,2-(benzo[d][1,3,2]dioxaborol-2-yl)pyridin-3-amine, and2-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)pyridin-3-amine.
 13. Acomposition according to claim 1, wherein said aromatic system whichcomprises at least one boronic acid or boronic ester moiety and which iscapable of forming upon oxidation a nucleophile or an electrophile isselected from the group consisting of 1H-indol-3-yl-3-boronic acid,5-amino-1H-indol-3-yl-3-boronic acid,5,6-dimethoxy-1H-indol-3-yl-3-boronic acid,5H-[1,3]dioxolo[4,5-f]indol-7-yl-7-boronic acid,5-amino-1H-indol-3-yl-3-boronic acid, 5-chloro-1H-indol-3-yl-3-boronicacid, 5-methoxy-1H-indol-3-yl-3-boronic acid,7-methoxy-1H-indol-3-yl-3-boronic acid, 4-fluoro-1H-indol-3-yl-3-boronicacid, 5-bromo-1H-indol-3-yl-3-boronic acid,4-methyl-1H-indol-3-yl-3-boronic acid, 6-methyl-1H-indol-3-yl-3-boronicacid, 3-(1,3,2-dioxaborolan-2-yl)-1H-indole,3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole,3-(4,5-dimethyl-1,3,2-dioxaborolan-2-yl)-1H-indole,3-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-1H-indole,3-(benzo[d][1,3,2]dioxaborol-2-yl)-1H-indole,5-bromo-3-(1,3,2-dioxaborolan-2-yl)-1H-indole,6-methoxy-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole, and5-methoxy-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole. 14.A composition according to claim 1, wherein said aromatic system whichcomprises at least one boronic acid or boronic ester moiety and which iscapable of forming upon oxidation a nucleophile or an electrophile isselected from the group consisting of 4-benzoyl-3-hydroxyphenylboronicacid, 4-(3,5-diaminobenzoyl)-3-hydroxyphenylboronic acid,4-(3,5-dihydroxybenzoyl)-3-hydroxyphenylboronic acid,4-(2,4-dihydroxybenzoyl)-3-hydroxyphenylboronic acid,4-(2,4-diaminobenzoyl)-3-hydroxyphenylboronic acid,4-(2,5-diaminobenzoyl)-3-hydroxyphenylboronic acid,4-(2,5-dihydroxybenzoyl)-3-hydroxyphenylboronic acid,4-(2,6-diaminobenzoyl)-3-hydroxyphenylboronic acid,4-(2,6-dihydroxybenzoyl)-3-hydroxyphenylboronic acid,(4-(1,3,2-dioxaborolan-2-yl)-2-hydroxyphenyl)(phenyl)methanone,(3,5-diaminophenyl)(2-hydroxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)methanone,(4-(1,3,2-dioxaborolan-2-yl)-2-hydroxyphenyl)(3,5-dihydroxyphenyl)methanone,(2-hydroxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)(2,4-dihydroxyphenyl)methanone,(4-(1,3,2-dioxaborolan-2-yl)-2-hydroxyphenyl)(2,4-diaminophenyl)methanone, and(2-hydroxy-4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)phenyl)(3,5-dihydroxyphenyl)methanone.15. A composition according to claim 1, wherein said aromatic systemwhich comprises at least one boronic acid or boronic ester moiety andwhich is capable of forming upon oxidation a nucleophile or anelectrophile is selected from the group consisting of2-benzoyl-3-hydroxyphenylboronic acid,2-(3,5-diaminobenzoyl)-3-hydroxyphenylboronic acid,2-(3,5-dihydroxybenzoyl)-3-hydroxyphenylboronic acid,(2-(1,3,2-dioxaborolan-2-yl)-6-hydroxyphenyl)(phenyl)methanone,(3,5-diaminophenyl)(2-hydroxy-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)methanone,(2-hydroxy-6-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)phenyl)(3,5-dihydroxyphenyl)methanone,(2,5-diaminophenyl)(2-hydroxy-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)methanone, and(2-hydroxy-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)(2,5-dihydroxyphenyl)methanone.16. A composition according to claim 1, wherein said aromatic systemwhich comprises at least one boronic acid or boronic ester moiety andwhich is capable of forming upon oxidation a nucleophile or anelectrophile is selected from the group consisting of2,5,6-triaminopyrimidin-4-yl-4-boronic acid,6-(1,3,2-dioxaborolan-2-yl)pyrimidine-2,4,5-triamine,6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrimidine-2,4,5-triamine,6-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)pyrimidine-2,4,5-triamine, and6-(benzo[d][1,3,2]dioxaborol-2-yl)pyrimidine-2,4,5-triamine.
 17. Acomposition according to claim 1, wherein said auxiliary developer isselected from the group consisting of 2-methyl-benzene-1,4-diamine,benzene-1,4-diamine, 2-thiazole-2-yl-benzene-1,4-diamine, 2-(6-methyl-pyridin-2-yl)-benzene-1,4-diamine, 3′-fluoro-biphenyl-2,5-diamine,2-propenyl-2-yl-benzene-1,4-diamine,2-(methoxymethyl)benzene-1,4-diamine,N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 4-amino-phenol,4-methylamino-phenol, 4-amino-3-methyl-phenol,1-hydroxy-2,4-diaminobenzene, 2-amino-phenol, 2-amino-5-methyl-phenol,2-amino-6-methyl-phenol, 1-methyl -1H-pyrazole-4,5-diamine,1-hydroxyethyl-4,5-diaminopyrazole sulphate,2-(4,5-diamino-1H-pyrazol-1-yl)ethanol, and mixtures thereof.
 18. Acomposition according to claim 1, wherein said auxiliary coupler isselected from the group consisting of benzene-1,3-diol,4-chlorobenzene-1,3-diol, 2-methyl-benzene-1,3-diol,benzene-1,3-diamine, 3-amino-phenol, 5-amino-2-methyl-phenol,1-methyl-2-hydroxy-4-(2′-hydroxyethyl)aminobenzene,4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, 2-aminopyridin-3-ol,1-phenyl-3-methylpyrazol-5-one,1-phenyl-3-methyl-5-pyrazolone-2,4-dihydro-5,2-phenyl-3H-pyrazole-3-one,and mixtures thereof.
 19. A composition according to claim 1, whereinsaid aromatic system which comprises at least one boronic acid orboronic ester moiety and which is capable of forming upon oxidation anucleophile or an electrophile acts as a coupler, and wherein saidauxiliary developer is a pyrazole developer selected from the groupconsisting of 1-methyl-1H-pyrazole-4,5-diamine,2-(4,5-diamino-1H-pyrazol-1-yl)ethanol,1-isopropyl-1H-pyrazole-4,5-diamine,1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine,1-(benzyl)-1H-pyrazole-4,5-diamine,1-(4-chlorobenzyl)-1H-pyrazole-4,5-diamine and 1-hydroxyethyl-4,5-diaminopyrazole sulfate.
 20. A composition accordingto claim 1, further comprising at least one additional componentselected from the group consisting of direct dyes, oxidizing agents,thickeners, chelants, pH modifiers, buffering agents, and carbonate ionsource and radical scavenger systems.
 21. A method of oxidatively dyeinghair, said method comprising the steps of: (a) mixing a compositionaccording to claim 1 with an oxidizing agent to form a mixture; (b)applying said mixture to the hair; and (c) rinsing the hair.
 22. A haircoloring product in kit form, said kit comprising: (a) a firstseparately packaged container comprising a composition according toclaim 1; and (b) a second separately packaged container comprising anoxidizing agent.